Process of producing natural or artificial fibers having dyeing properties resembling those of wool and products obtained thereby



Patented 'Feb. 18, 1941 PATENT OFFICE rnocsss or PRODUCING NATURALARTIFICIAL FIBERS HAVING DYEING PROPERTIES RESEMBLING' THOSE OF WOOLANDPRODUCTS OBTAINED THERE- Panl Essclmann, Wolfen, Kreis Bitterfeld, andJosef Diising, Dessau, Germany, assignors, by mesne assignments, toWalther H. Duisberg,

New York, N. Y.

No Drawing. Application December 7, 1938, Serial No. 244,388. In GermanyAugust 4, 1937 5 Claims.

Our-present invention relates to the production of fibers, foils,threads, ribbons and the like materials which are capable of being dyedwith acid wool dyestufis.

We have previously disclosed in our application Ser. No. 223,012, filedAugust 4, 1938, that it is possible to produce artificialtextilematerials,

capable of being dyed with acid wool dyestuffs in the same manner aswool. by incorporating and finely dispersing in the solutions from whichthe textile materials are to be formed a synthetic resinous compositionstable against dilute acids and alkalies which resinous composition isthe product of the joint polymerizationof an alkylene imine and aprotein and an anate or an arylisothiocyanate.

By the present application which is a continuationin part of theaforesaid application Ser. No. 223,012 we extend the application of thesaid resinous compositions also to natural cellulosic fibers and toartificial fibers in such cases where it is not desirable or possible tointroduce or finely disperse the resinous compositions in the spinningsolutions.

The present invention therefore has for an.

base, a solution of an albuminous substance, a

solution ofan arylisocyanate or an arylisothiocyanate and heating theimpregnated fibers to a temperature sumciently elevated to causepolymerization of the alkylene imine with the isocyanate, fibers areobtained which have exactly the character of wool as regards thecapacity of being dyed with acid dyes and the fastness of the dyeings towashing and to light. We are aware that processes of impregnating fiberswith various substances including resins have been pro- P sed. Thedyeings on the fibers hitherto pro-- duced according to these processeshave been unable to satisfy practical requirements as re gardsproperties of fastness in all respects. Contrary to these prior artproposals the. present invention provides fibers whichare characterizedby suflicient fastness to washing, perspiration,

arylisocyrubbing and other friction, and satisfactory fastness to light.

Fibers which have been made from casein'so- 'lutions of course do notneed an additional impregnation with an albuminous substance. In thesecases it is suflicient to impregnate the artificial fibers with alkyleneimines and the aromatic isocyanate. resin may be produced on the fibersby polymerization which can be effected by heating. The dyeings withwool dyestufis on casein fibers in this manner are essentially fasterthan dyeings on ordinary casein fibers which have not been impregnatedwith .the resins.

The fibers may be impregnated with the finished resinous compositions insolution whereafter further condensation on the fibers is effected by ashort additional heating. On the other hand they may be impregnated withthe constituents of the resin and condensation may be effected on thefibers by heating and drying.

Suitable starting materials for the polymerization have been describedin our copending U. S. patent application Ser. No. 223,013 file August4, 1938.

The following may be mentioned as examples. Suitable organic bases are,for instance, the

alkyleneimines, such as ethylene-, propyleneand butylene-imines,N-propyl-ethyleneimine and N-benzylethyleneimine.

Furthermore aliphatic and aromatic amines,

such as methylamine, stearylamine and aniline may be employed.

Suitable protein substances are casein, albumen, gelatin, and the likematerials.

As arylisoand arylisothiocyanates there may be employed mainly thephenyland naphthylisocyanates as Well as the phenylandnaphthylisothiocyanates, benzylisocyanate, and related compounds.

The following examples serve to illustrate the invention.

Example! Fibers made from casein or fibers containing casein areimmersed in a benzene solution of per cent strength of ethyleneimine'and led through the solution several times by means of creasing rollers.,After the ethyleneimine solution has acted upon the fibers for about 30minutes the adhering liquid is'removed from the fibers, if necessary bycentrifuging, and they are immersed in a solution of phenylisocya'natefor a few minutes. The fibers are. then removed from thephenylisocyanate solution. Thereupon they After the impregnation the areadvantageously washed once more in soap water.

Example 2 A strand of cotton is immersed in a solution of 1 part ofcasein, 5 parts of an aqueous ethyleneimine solution of 30 per centstrength and 5 parts of phenylisocyanate. The impregnated cotton threadsare centrifuged and heated for an hour at a temperature of 7 C. Apolymerization product is formed on and in the cotton fibers whichadheres strongly thereto and cannot be removed by scouring and washing.The cotton fibers acquire a distinct affinity for acid dyestuffs 'suchas .for instance Palatine Fast Blue BR (Schultz Farbstofltabellen, volII, 7th edition, page 168) Supramine Red B (Schultz Farbstofitabellen,vol. II, 7th edition, page 203), Acid Antracene Red 3 BL (SchultzFarbstofi-tabellen, Suppl. vol. I, 7th edition, page 125) and metachromedyestuffs. The dyeings on these fibers are absolutely fast to light.

Example 3 Rayon staple fibers in the form of yarns or threads areimmersed into a solution of ethyleneimine and casein in a proportion ofcasein to ethyleneimine of 1 in 3. The threads are centrifuged to removeexcess liquid and immersed into a solution of phenylisocyanate incyclohexanol. The threads are again centrifuged and inserted into adrying apparatus at a temperature of 80 C. for an hour. The fibers thusobtained may be dyed in one bath together with wool fibers from theclass consisting of arylisocyanates and arylisothiocyanates and heatingthe impregnated fibers until they are completely dry, whereby jointpolymerization of the constituents with formation of a resin occurs.

2. A process of producing fibers, films, foils, ribbons and the likematerials capable of being ,dyed by acid wool dyestufis which processcomprises impregnating a textile material having per se insufiicientaflinity for acid dyes with a solution of a mixture of a protein and analkylene imine, immersing the impregnated textile materials into tnesolution of a member selected from the class consisting ofarylisocyanate and arylisothiocyanates and heating said textilematerials to a temperature sufiiciently elevated to cause jointpolymerization of the constituents with formation of a resin.

3. A process of producing fibers, films, foils, ribbons and the likematerials capable of being dyed by acid wool dyestuffs which processcomprises impregnating a textile material having per se insuificientafiinity for acid dyes with a solution of ethyleneimine and casein,immersing the impregnated textile materials into a solution ofphenylisocyanate and heating the textile materials to a temperature offrom 60 to 100 C. until said textile materials are completely dried,whereby joint polymerization of the constituents with formation of aresin occurs.

4. Textile materials impregnated with a resin being the product of ajoint polymerization of one alkylene imine, a protein and a compoundselected from the class consisting of arylisocyanates andarylisothiocyanates, which resin is substantially insoluble in acids andalkalies and imparts to said textile materials aflinity for acid dyes.

5. Textile materials impregnated with the resin produced by jointlypolymerizing ethylene imine, casein, and phenylisocyanate, which resinis substantially insoluble in acids and alkalies and imparts to saidtextile materials affinity for acid dyes.

PAUL ESSELMANN.

JOSEF. iisING.

